Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0066—Flame-proofing or flame-retarding additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/02—Halogenated hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
  • C08K5/3477—Six-membered rings
  • C08K5/3492—Triazines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
  • C08K5/3477—Six-membered rings
  • C08K5/3492—Triazines
  • C08K5/34928—Salts
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds

Definitions

• the instant invention in particular pertains to a method of flame retarding polyolefins such as polypropylene and polyethylene.
• U.S. Pat. No. 4,504,611 teaches flame retardant polyamide comprising zinc borate, melamine cyanurate and certain organohalogens.
• GB 2085898 discloses flame retardant polyolefin comprising aromatic bromo hydrocarbon (DBDPO), an antimony or bismuth compound, an organic compound, and a triazine derivative (e.g. melamine).
• DBDPO aromatic bromo hydrocarbon
• an antimony or bismuth compound an organic compound
• a triazine derivative e.g. melamine
• JP 57070152 teaches flame retardant epoxy resins which contain antimony trioxide, an orgaonobromine compound and a melamine-cyanuric acid adduct.
• JP 58101128 teaches flame retardant epoxy resin, phenol resin, thermoset polyester resin or polyurethane resin, which contain antimony trioxide, organohalogen compound, melamine-cyanuric acid product, melamine-phosphoric acid product and melamine-molybdic acid product.
• U.S. Pat. No. 5,356,568 teaches flame retardant coatings that comprise phosphorus-containing material (e.g. melamine phosphate) and a halogen-containing material (e.g. chlorinated paraffin).
• phosphorus-containing material e.g. melamine phosphate
• halogen-containing material e.g. chlorinated paraffin
• JP 10176095 discloses flame retardant polystyrene comprising organohalogen compounds and ammonium polyphosphates and/or triazine phosphates (e.g. melamine phosphate) and a drip-proof agent.
• polymers with good flame retardant properties for example polyolefins, are prepared when a melamine based flame retardant is added thereto together with an organohalogen flame retardant or a phosphorus containing flame retardant.
• the instant invention pertains to a flame retardant polymer composition which comprises
• the mixture of (i) and (ii) is in many instances synergistic towards providing flame retardancy.
• compositions of this invention may further include flame retardant fillers and/or conventional fillers.
• Flame-retardant fillers are known in the art and are selected from the group consisting of magnesium hydroxide, alumina trihydrate and zinc borate. Flame-retardant fillers are inorganic compounds employed for flame-retardant properties, and at high enough levels to be considered “filler”. Conventional fillers such as talc, calcium carbonate and the like are normally employed for instance for flow properties in order to reduce the spread of flaming droplets (not flame-retardant per se).
• compositions of this invention may further include nano-scaled fillers.
• Nano-scaled fillers are also referred to as “nanoclays” are disclosed for example in U.S. Pat. Nos. 5,853,886 and 6,020,419, the relevant disclosures of which are hereby incorporated by reference.
• Nano-scaled fillers of the present invention are for example phyllosilicates or smectite clays, for example organophilic phyllosilicates, naturally occuring phyllosilicates, synthetic phyllosilicates or a mixture of such phyllosilicates.
• the present nano-scaled fillers are for example montmorillonites, bentonites, beidellites, hectorites, saponites or stevensites.
• the present compositions may further advantageously include antimony compounds such as antimony trioxide (Sb 2 O 3 ) or antimony pentoxide (Sb 2 O 5 ).
• the antimony compounds may be present from about 0.5% to about 8% by weight, based on the weight of the polymer substrate.
• the antimony compounds may be present from about 1% to about 6% by weight, or from about 2% to about 5% by weight, based on the weight of the polymer substrate.
• the antimony compounds may be present at about 2%, 3%, 4% or 5% by weight, based on the weight of the polymer substrate.
• compositions may further advantageously include sterically hindered amine stabilizers.
• the sterically hindered amines may be present from about 0.1% to about 10% by weight, based on the weight of the polymer substrate.
• the present compositions may include both antimony compounds and sterically hindered amine stabilizers.
• compositions may advantageously include acid scavengers.
• Acid scavengers are for example hydrotalcites and amorphous basic aluminum magnesium carbonates, such as those described in U.S. Pat. Nos. 4,427,816, 5,106,898 and 5,234,981, the relevant disclosures of which are hereby incorporated by reference.
• Hydrotalcite is, also known as hycite or DHT4A.
• Hydrotalcites are natural or synthetic.
• the natural hydrotalcite is held to possess a structure Mg 6 Al 2 (OH) 16 CO 3 .4 H 2 O.
• a typical empirical formula of a synthetic hydrotalcite is Al 2 Mg 4.35 OH 11.36 CO 3(1.67) .x H 2 O.
• Examples of the synthetic product include: Mg 0.7 Al 0.3 (OH) 2 (CO 3 ) 0.15 .0.54 H 2 O, Mg 4.5 Al 2 (OH) 13 CO 3 .3.5 H 2 O and Mg 4.2 Al(OH) 12.4 CO 3 .
• the present compositions meet requirements of UL 1694 Tests for Flammability of Small Polymeric Component Materials, 2002.
• the present compositions also meet requirements of UL 94 Tests for Flammability of Plastic Materials for Parts in Devices and Appliances.
• compositions also exhibit excellent physical properties as exhibited by tensile strength and/or impact strength.
• the present compositions do not require organic radical sources to meet for example a V-0, V-1 or a V-2 threshold according to UL 94, or to meet a SC-0, SC-1 or SC-2 level according to UL 1694.
• the organic radical sources are for example compounds of formula (1) according to GB 2085898, for example (2,3-dimethyl-2,3-diphenyl)-hexane or -butane.
• Meeting V-0, V-1 or V-2 according to UL 94, or meeting SC-0, SC-1 or SC-2 according to UL 1694 is considered “passing” UL 94 or UL 1694 respectively.
• R CH 3 or C 2 H 5
• R′ CH 3
• R′′ C 6 H 5
• compositions comprise essentially no organic radical sources, or comprise no organic radical sources.
• Both clear and pigmented polymer compositions meet V-0, V-1 or V-2 according to UL 94 or SC-0, SC-1 or SC-2 according to UL 1694.
• compositions also meet V-0, V-1 or V-2 according to UL-94 or SC-0, SC-1 or SC-2 according to UL 1694 after weathering exposure (ultraviolet light exposure), for example after exposure to 1000 hours in a xenon arc WeaterOmeter, Atlas Cl 65A xenon arc WeaterOmeter, ASTM G26 test method A. After exposure, the compositions also retain at least 75% of izod impact strength and tensile strength.
• compositions also meet V-0, V-1 or V-2 or SC-0, SC-1 or SC-2 performance levels according to UL 94 or UL 1694 respectively, after exposure to water, for example after immersion in water for 7 days at 70° C. After water immersion, the samples also retain at least 50% of izod impact strength and tensile strength.
• the present compositions also meet V-0, V-1 or V-2 or SC-0, SC-1 or SC-2 performance levels according to UL 94 or UL 1694 respectively, after thermal exposure, for example after oven aging at different elevated temperatures (130, 140, 150 and 160° C. for 9000 hrs, 5000 hrs, 2500 hrs and 1000 hrs, respectively), or at 90C for 2000 hours.
• the oven is a regular air forced oven. After the exposure, the samples also retain at least 65% of physical properties such as izod impact and tensile strength.
• the compositons are for example polypropylene homopolyer plaques comprising the present flame retardant additives, for example 1.6 mm plaques.
• the polypropylene plaques are clear or pigmented, for instance white or green pigmented.
• the polymer substrate is selected from the group of resins consisting of the polyolefins, the thermoplastic olefins, styrenic polymers and copolymers, and ABS.
• polymer substrate is selected from the group consisting of polypropylene, polyethylene, thermoplastic olefin (TPO), ABS and high impact polystyrene.
• the polymer substrate is polypropylene, polyethylene or thermoplastic olefin (TPO).
• Organic polymers of component A are for example thermoplastic polymers such as polyolefins like polyethylene, polypropylene or copolymers thereof.
• the thermoplastic polymer is for example polypropylene.
• organic polymers are:
• Polymers of monoolefins and diolefins for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyvinylcyclohexane, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).
• HDPE high density polyethylene
• HDPE-HMW high density and high molecular weight polyethylene
• HDPE-UHMW high density and ultrahigh molecular weight polyethylene
• MDPE medium density polyethylene
• LDPE low density
• Copolymers of monoolefins and diolefins with each other or with other vinyl monomers for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin copolymers (e.g.
• ethylene/norbornene like COC ethylene/1-olefins copolymers, where the 1-olefin is generated in-situ; propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/vinylcyclohexene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers or ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1) above, for example polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetate copoly
• Polystyrene poly(p-methylstyrene), poly( ⁇ -methylstyrene).
• Hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned under 6. especially including polycyclohexylethylene (PCHE) prepared by hydrogenating atactic polystyrene, often referred to as polyvinylcyclohexane (PVCH).
• PCHE polycyclohexylethylene
• PVCH polyvinylcyclohexane
• Homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; for example atactic polymers.
• Stereoblock polymers are also included.
• Graft copolymers of vinyl aromatic monomers such as styrene or ⁇ -methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpolymers; st
• Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
• halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated
• Polymers derived from ⁇ , ⁇ -unsaturated acids and derivatives thereof such as polyacrylates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles, impact-modified with butyl acrylate.
• Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers for example acrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.
• Polymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals thereof for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral; polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1) above.
• Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
• Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol
• Polyureas Polyureas, polyimides, polyamide-imides, polyetherimids, polyesterimids, polyhydantoins and polybenzimidazoles.
• Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones for example polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate (PAN) and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS.
• Blends of the aforementioned polymers for example PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.
• polyblends for example PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS
• the melamine based flame retardants are for example:
• Oganohalogen flame retardants are for example:
• the phosphorus containing flame retardants are for example:
• Boric acid may be included as a further flame retardant.
• halogenated flame retardants useful in the present invention may be selected from organic aromatic halogenated compounds such as halogenated benzenes, biphenyls, phenols, ethers or esters thereof, bisphenols, diphenyloxides, aromatic carboxylic acids or polyacids, anhydrides, amides or imides thereof; organic cycloaliphatic or polycycloaliphatic halogenated compounds; and organic aliphatic halogenated compounds such as halogenated paraffins, oligo- or polymers, alkylphosphates or alkylisocyanurates.
• organic aromatic halogenated compounds such as halogenated benzenes, biphenyls, phenols, ethers or esters thereof, bisphenols, diphenyloxides, aromatic carboxylic acids or polyacids, anhydrides, amides or imides thereof
• organic cycloaliphatic or polycycloaliphatic halogenated compounds organic aliphatic halogenated compounds such
• phosphazene flame retardants are well known in the art. They are disclosed for example in EP1104766, JP07292233, DE19828541, DE1988536, JP11263885, U.S. Pat. Nos. 4,107,108, 4,108,805 and 4,079,035 and 6,265,599. The relevant disclosures of the U.S. Patents are hereby incorporated by reference.
• PTFE polytetrafluoroethylene
• Teflon® 6C E. I. Du Pont
• component (b) is present at about 15%, 16%, 17%, 18%, 19% or about 20%, based on the weight of the polymer substrate.
• component (b) is employed from about 0.5% to about 12%, from about 0.5% to about 10%, from about 0.5% to about 8%, or from about 0.5% to about 6% by weight, based on the weight of the polymer substrate.
• the ratio (parts by weight) of component (i) to component (ii) is for example between about 100:1 to about 1:100, for instance from about 50:1 to about 1:50, or about 10:1 to about 1:10, or about 5:1 to about 1:5.
• the ratio of component (i) to component (ii) is from about 100:1 to about 1:50, from about 100:1 to about 1:10, or from about 100:1 to about 1:5.
• the weight ratio of component (i) to component (ii) is from about 1:100 to about 50:1, from about 1:100 to about 10:1, or from about 1:100 to about 5:1.
• the weight ratio of component (i) to component (ii) is about 1:4, 1:3, 1:2, 1:1, 2:1, 3:1 or 4:1.
• the weight ratio of component (i) to component (ii) is from about 1:1 to about 1:2.
• the amount of component (ii) used also depends on the effectiveness of the specific compound(s), the polymer and the specific application type.
• the present hindered amines are for example monomeric compounds or are oligomeric or polymeric compounds.
• Hindered alkoxyamine stabilizers are well known in the art, also known as N-alkoxy hindered amines and NOR hindered amines or NOR hindered amine light stabilizers or NOR HALS.
• U.S. Pat. Nos. 6,271,377, 6,392,041 and 6,376,584 cited above disclose hindered hydroxyalkoxyamine stabilizers.
• the hindered hydoxyalkoxyamine stabilizers are considered a subset of the hindered alkoxyamine stabilizers.
• Hindered hydroxyalkoxyamine stabilizers are also known as N-hydroxyalkoxy hindered amines, or NORol HALS.
• Suitable hindered amines according to the present invention include for example:
• n is from 1 to 15;
• the optional hindered amine stabilizers are advantageously contained in the composition of the invention in an amount from about 0.05% to about 20% by weight based on the polymer substrate (a); for example from about 0.1% to about 10% by weight; for example from about 0.2% to about 8% by weight; for instance from about 0.5% to about 3% by weight.
• the stabilizers of component (i) are present from about 0.05% to about 15%, from about 0.05% to about 10%, from about 0.05% to about 8%, from about 0.05% to about 5% or from about 0.05% to about 3% by weight based on the weight of substrate (a).
• the stabilizers of component (i) are present from about 0.1% to about 20%, from about 0.2 to about 20%, from about 0.5 to about 20% or from about 1% to about 20% by weight based on the weight of substrate (a).
• compositions of the present invention are useful for many applications, for example outdoor applications, including the following:
• the materials containing the stabilizers described herein can be used for the production of moldings, rotomolded articles, injection molded articles, blow molded articles, mono- and multilayer films, extruded profiles, surface coatings and the like.
• compositions of the invention may optionally also contain various conventional additives, for example in amounts from about 0.01 to about 10%, for instance from about 0.025 to about 4%, for example from about 0.1 to about 2% by weight of component (a), such as the materials listed below, or mixtures thereof.
• Alkylated monophenols for example 2,6-di-tert-butyl4-methylphenol, 2-tert-butyl4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-( ⁇ -methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linear or branched in the side chains, for example, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1′-methylundec-1′-yl)phenol, 2,4-di
• Alkylthiomethylphenols for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol.
• Hydroquinones and alkylated hydroquinones for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octade-cyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis-(3,5-di-tert-butyl-4-hydroxyphenyl)adipate.
• 2,6-di-tert-butyl-4-methoxyphenol 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4
• Tocopherols for example ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol and mixtures thereof (Vitamin E).
• Hydroxylated thiodiphenyl ethers for example 2,2′-thiobis(6-tert-butyl4-methylphenol), 2,2′-thiobis(4-octylphenol), 4,4′-thiobis(6-tert-butyl-3-methylphenol), 4,4′-thiobis(6-tert-butyl-2-methylphenol), 4,4′-thiobis-(3,6-di-sec-amylphenol), 4,4′-bis(2,6-dimethyl4-hydroxyphenyl)disulfide.
• 2,2′-thiobis(6-tert-butyl4-methylphenol 2,2′-thiobis(4-octylphenol), 4,4′-thiobis(6-tert-butyl-3-methylphenol), 4,4′-thiobis(6-tert-butyl-2-methylphenol), 4,4′-thiobis-(3,6-di-sec-amylphenol), 4,4′-bis(2,6
• Alkylidenebisphenols for example 2,2′-methylenebis(6-tert-butyl-4-methylphenol), 2,2′-methylenebis(6-tert-butyl-4-ethylphenol), 2,2′-methylenebis[4-methyl-6-( ⁇ -methylcyclohexyl)-phenol], 2,2′-methylenebis(4-methyl-6-cyclohexylphenol), 2,2′-methylenebis(6-nonyl-4-methylphenol), 2,2′-methylenebis(4,6-di-tert-butylphenol), 2,2′-ethylidenebis(4,6-di-tert-butylphenol), 2,2′-ethylidenebis(6-tert-butyl4-isobutylphenol), 2,2′-methylenebis[6-( ⁇ -methylbenzyl)-4-nonylphenol], 2,2′-methylenebis[6-( ⁇ , ⁇ -dimethylbenzyl)-4-nonylphenol
• O—, N— and S-benzyl compounds for example 3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
• S-benzyl compounds for example 3,5,3′,5′-tetra-tert-butyl-4,4′-
• Hydroxybenzylated malonates for example dioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate, di-dodecylmeraptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
• Aromatic hydroxybenzyl compounds for example 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
• Triazine Compounds for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,6-tri-tri
• Benzylphosphonates for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
• Acylaminophenols for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
• esters of ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[
• esters of ⁇ -(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N′-bis-(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[
• esters of ⁇ -(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
• esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
• Aminic antioxidants for example N,N′-di-isopropyl-p-phenylenediamine, N,N′-di-sec-butyl-p-phenylenediamine, N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N′-bis(1-methylheptyl)-p-phenylenediamine, N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine, N,N′-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N′-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N′-phenyl-p-
• 2-Hydroxybenzophenones for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxy and 2′-hydroxy4,4′-dimethoxy derivatives.
• Esters of substituted and unsubstituted benzoic acids as for example 4-tertbutyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl) resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
• Acrylates for example ethyl ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate, isooctyl ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate, methyl ⁇ -carbomethoxycinnamate, methyl ⁇ -cyano- ⁇ -methyl-p-methoxy-cinnamate, butyl ⁇ -cyano- ⁇ -methyl-p-methoxy-cinnamate, methyl ⁇ -carbomethoxy-p-methoxycinnamate and N-( ⁇ -carbomethoxy- ⁇ -cyanovinyl)-2-methylindoline.
• Nickel compounds for example nickel complexes of 2,2′-thio-bis-[4-(1,1,3,3-tetramethyl-butyl)phenol], such as the 1:1 or 1:2 complex, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes of ketoximes, e.g. of 2-hydroxy4-methylphenyl undecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.
• additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarba
• Sterically hindered amines for example bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl4-piperidyl)succinate, bis(1,2,2,6,6-pentamethyl4-piperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensates of N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6
• Oxamides for example 4,4′-dioctyloxyoxanilide, 2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide, 2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide, N,N′-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with 2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
• Tris-aryl-o-hydroxyphenyl-s-triazines for example known commercial tris-aryl-o-hydroxyphenyl-s-triazines and triazines as disclosed in, WO 96/28431 and U.S. Pat. Nos.
• Metal deactivators for example N,N′-diphenyloxamide, N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl) hydrazine, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyl dihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.
• Phosphites and phosphonites for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis
• Tris(2,4-di-tert-butylphenyl)phosphite (Irgafos® 168, Ciba-Geigy), tris(nonylphenyl)phosphite,
• Hydroxylamines for example, N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
• Nitrones for example, N-benzyl-alpha-phenyl-nitrone, N-ethyl-alpha-methyl-nitrone, N-octyl-alpha-heptyl-nitrone, N-lauryl-alpha-undecyl-nitrone, N-tetradecyl-alpha-tridcyl-nitrone, N-hexadecyl-alpha-pentadecyl-nitrone, N-octadecyl-alpha-heptadecyl-nitrone, N-hexadecyl-alpha-heptadecyl-nitrone, N-ocatadecyl-alpha-pentadecyl-nitrone, N-heptadecyl-alpha-heptadecyl-nitrone, N-octadecyl-alpha-hexadecyl-nitrone, nitro
• Thiosynergists for example, dilauryl thiodipropionate or distearyl thiodipropionate.
• Peroxide scavengers for example esters of ⁇ -thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercapto-benzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis( ⁇ -dodecylmercapto)propionate.
• esters of ⁇ -thiodipropionic acid for example the lauryl, stearyl, myristyl or tridecyl esters
• mercaptobenzimidazole or the zinc salt of 2-mercapto-benzimidazole zinc dibutyldithiocarbamate
• dioctadecyl disulfide pentaerythritol tetrakis( ⁇ -dodecyl
• Polyamide stabilizers for example, copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
• Nucleating agents for example, inorganic substances such as talcum, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, for example, alkaline earth metals; organic compounds such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds such as ionic copolymers (ionomers).
• inorganic substances such as talcum, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, for example, alkaline earth metals
• organic compounds such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate
• polymeric compounds such as ionic copolymers (ionomers
• Fillers and reinforcing agents for example, calcium carbonate, silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers.
• additives for example, plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents.
• Benzofuranones and indolinones for example those disclosed in U.S. Pat. Nos. 4,325,863; 4,338,244; 5,175,312; 5,216,052; 5,252,643; DE-A-4316611; DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102 or 3-[4-(2-acetoxyethoxy)-phenyl]-5,7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one, 3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one], 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-
• Amine oxides for example amine oxide derivatives as disclosed in U.S. Pat. Nos. 5,844,029 and 5,880,191, didecyl methyl amine oxide, tridecyl amine oxide, tridodecyl amine oxide and trihexadecyl amine oxide.
• thermoplastic compositions may further contain a stabilizer or mixture of stabilizers selected from phenolic antioxidants, hindered amine light stabilizers, ultraviolet light absorbers, organic phosphorus compounds, alkaline metal salts of fatty acids and thiosynergists.
• a stabilizer or mixture of stabilizers selected from phenolic antioxidants, hindered amine light stabilizers, ultraviolet light absorbers, organic phosphorus compounds, alkaline metal salts of fatty acids and thiosynergists.
• additives which are benzofuran-2-ones, such as described, for example, in U.S. Pat. Nos. 4,325,863, 4,338,244 or 5,175,312.
• additional components are selected from pigments, dyes, plasticizers, antioxidants, thixotropic agents, levelling assistants, basic costabilizers, further light stabilizers like UV absorbers and/or sterically hindered amines, metal passivators, metal oxides, organophosphorus compounds, hydroxylamines, and mixtures thereof, especially pigments, phenolic antioxidants, calcium stearate, zinc stearate, UV absorbers of the 2-(2′-hydroxyphenyl)benzotriazole and 2-(2-hydroxyphenyl)-1,3,5-triazine classes, and sterically hindered amines.
• the additives of the invention and optional further components may be added to the polymer material individually or mixed with one another. If desired, the individual components can be mixed with one another before incorporation into the polymer for example by dry blending, compaction or in the melt.
• Subject of the invention therefore is also a flame retardant additive combination comprising
• the additives of above components (i) and (ii) and possibly further additives as described above may be dry blended and then extruded, for instance in a twin screw extruder at 180–220° C., with or without nitrogen atmosphere.
• the material thus obtained may be further processed according to known methods.
• the surface of the articles formed do not show any loss of gloss or any kind of roughness.
• the instant invention pertains to a process for imparting flame retardancy to an organic polymer substrate, which process comprises adding to said polymer substrate an effective flame retarding amount of a mixture of
• the incorporation of the additives of the invention and optional further components into the polymer is carried out by known methods such as dry blending in the form of a powder, or wet mixing in the form of solutions, dispersions or suspensions for example in an inert solvent, water or oil.
• the additives of the invention and optional further additives may be incorporated, for example, before or after molding or also by applying the dissolved or dispersed additive or additive mixture to the polymer material, with or without subsequent evaporation of the solvent or the suspension/dispersion agent. They may be added directly into the processing apparatus (e.g. extruders, internal mixers, etc), e.g. as a dry mixture or powder or as solution or dispersion or suspension or melt.
• the addition of the additive or additive blend to the polymer can be carried out in all customary mixing machines in which the polymer is melted and mixed with the additives. Suitable machines are known to those skilled in the art. They are predominantly mixers, kneaders and extruders.
• processing machines are single-screw extruders, contrarotating and corotating twin-screw extruders, planetary-gear extruders, ring extruders or cokneaders. It is also possible to use processing machines provided with at least one gas removal compartment to which a vacuum can be applied.
• the maximum throughput is dependent on the screw diameter, the rotational speed and the driving force.
• the process of the present invention can also be carried out at a level lower than maximum throughput by varying the parameters mentioned or employing weighing machines delivering dosage amounts.
• the additives of the invention and optional further additives can also be sprayed onto the polymer material. They are able to dilute other additives (for example the conventional additives indicated above) or their melts so that they can be sprayed also together with these additives onto the material. Addition by spraying during the deactivation of the polymerization catalysts is particularly advantageous; in this case, the steam evolved may be used for deactivation of the catalyst. In the case of spherically polymerized polyolefins it may, for example, be advantageous to apply the additives of the invention, optionally together with other additives, by spraying.
• the additives of the invention and optional further additives can also be added to the polymer in the form of a masterbatch (“concentrate”) which contains the components in a concentration of, for example, about 1% to about 40%, for example about 2% to, about 20% by weight incorporated in a polymer.
• concentration a masterbatch
• the polymer must not be necessarily of identical structure than the polymer where the additives are added finally.
• the polymer can be used in the form of powder, granules, solutions, suspensions or in the form of latices.
• Incorporation can take place prior to or during the shaping operation.
• the materials containing the additives of the invention described herein are for example used for the production of molded articles, for example rotomolded articles, injection molded articles, profiles and the like.
• the polyolefin molded articles of this invention may be used for example as roofing membranes, siding, window profiles and moldings. Such molded articles are for example about 5 mil to about 100 mil thick, for example about 20 mil to about 100 mil thick, for instance about 10 mil to about 80 mil for example about 40 mil to about 100 mil thick.
• the polyolefin is in particular thermoplastic olefin (TPO).
• the effective flame retarding amount of component (b) is that needed to show flame retarding efficacy as measured by one of the standard methods used to assess flame retardancy. These include UL 1694 Tests for Flammability of Small Polymeric Component Materials, 2002; NFPA 701 Standard Methods of Fire Tests for Flame-Resistant Textiles and Films, 1989 and 1996 and 1999 editions; the UL 94 Test for Flammability of Plastic Materials for Parts in Devices and Appliances, 5th Edition, Oct. 29, 1996; Limiting Oxygen Index (LOI), ASTM D-2863; and Cone Calorimetry, ASTM E-1354. Ratings according to the UL 94 V test are as compiled in the following table:
• Coadditives found particularly useful for use with the instant combination of components (i) and (ii) in flame retardant compositions are as follows:
• room temperature depicts a temperature in the range 20–25° C. Percentages are by weight of the polymer substrate unless otherwise indicated.
• R 1 , R 2 , R 3 and R 4 is hydrogen
• n is from 1 to 15;
• NOR2 NOR7, NOR11, NOR12 are commercial stabilizers available from Ciba Specialty Chemicals.
• MELAPUR products are available from Ciba Specialty Chemicals.
• Additives are dry mixed and extruded with polypropylene homopolymer resin with a twin screw (27 mm) extruder at 200° C. under nitrogen. From the pellets, 1.6 mm plaques are prepared by injection molding. The plaques are tested according to UL 94 protocol after 48 hours conditioning at 25° C. and 50% humidity and also after 7 days at 70° C. UL 94 ratings are the same for both exposures. The plaques are also tested according to UL 1694 protocol after 48 hours at 25° C. and 50% humidity and also after 24 hours at 70° C. UL 1694 ratings are the same for both exposures. Weight percent of additives and flame retardant results are in the table below. Weight percents are based on the polymer.
• NOR1–NOR13 The additional inclusion of a hindered amine selected from NOR1–NOR13 provides further flame retardancy as well as light stability.
• Melamine cyanurate may be replaced with a flame retardant selected from the group consisting of melamine borate, melamine phosphate, melamine polyphosphate, melamine pyrophosphate, melamine ammonium polyphosphate and melamine ammonium pyrophosphate with good results.
• a flame retardant selected from the group consisting of melamine borate, melamine phosphate, melamine polyphosphate, melamine pyrophosphate, melamine ammonium polyphosphate and melamine ammonium pyrophosphate with good results.
• FR1 and FR3 may be replaced with another flame retardant selected from FR1–FR9 with good results.
• Sample preparation Polymer powder and stabilizers are pre-mixed (Henschel mixer, 800 rpm, room temperature), pigment powder and flame retardant are added as concentrate in PP and homogenized in a drum mixer. Further homogenization and granulation is achieved by extrusion (Collin® twin screw extruder, max 200° C., 100 rpm). Subsequently, the mixture is processed into a flat film by means of a single screw extruder (max 200° C., 70 rpm) equipped with a corresponding nozzle (sample dimension 2 mm thickness, 10 cm width).
• Melamine cyanurate may be replaced with a flame retardant selected from the group consisting of melamine borate,melamine phosphate, melamine polyphosphate, melamine pyrophosphate, melamine ammonium polyphosphate and melamine ammonium pyrophosphate with good results.
• a flame retardant selected from the group consisting of melamine borate,melamine phosphate, melamine polyphosphate, melamine pyrophosphate, melamine ammonium polyphosphate and melamine ammonium pyrophosphate with good results.
• the polyolefin molded articles of this invention may be used for example as roofing membranes, siding, window profiles and moldings. Such molded articles are for example about 5 mil to about 100 mil thick.
• the polyolefin is in particlular thermoplastic polyolefin (TPO).
• TPO particlular thermoplastic polyolefin
• the molded articles of this invention exhibit flame retardant properties.
• Polypropylene copolymer 100 TiO 2 or carbon black 3 CaCo 3 5 Magnesium hydroxide 35 UV stabilizer 1 Lubricant or other 1
• the state of the art formulation requires that either TiO 2 or carbon black are present and that magnesium hydroxide is present.
• the formulation of the present invention is for example:
• NOR7 may be replaced for example with another hindered amine selected from NOR1–NOR13.
• FR1 may be replaced with a flame retardant selected from FR2–FR9. Excellent results are achieved.
• Melamine cyanurate may be replaced with a flame retardant selected from the group consisting of melamine borate, melamine phosphate, melamine polyphosphate, melamine ammonium polyphosphate, melamine ammonium pyrophosphate and melamine pyrophosphate with good results.
• a flame retardant selected from the group consisting of melamine borate, melamine phosphate, melamine polyphosphate, melamine ammonium polyphosphate, melamine ammonium pyrophosphate and melamine pyrophosphate with good results.
• Polyethylene fibers are prepared from fiber grade polyethylene by dry blending with test additives and melt compounding at 400° F. Fibers are extruded from this formulation using a Hills laboratory scale fiber extruder. Socks are knitted from the fibers and are tested for flame retardancy according to NFPA 701 vertical burn method. Polyethylene fibers contain 12% by weight of a 1:1 mixture of a melamine based flame retardant and a flame retardant selected from FR1–FR9 and 0.5%, 1% or 2% by weight, total, of an additive selected from NOR1–NOR13. These formulated fibers are tested for flame retardancy according to NFPA 701.
• the fibers containing a melamine based flame retardant, and a flame retardant selected from FR1–FR9 exhibit excellent flame retardancy.
• Foam grade polyethylene is dry blended with test additives and then melt compounded into pellets. The pelletized fully formulated resin is then blown into foam.
• the polyethylene foam prepared contains an instant additive selected from the melamine based flame retardants and a flame retardant FR1–FR9.
• the formulated foam is tested for flame retardancy according to the UL-94 burn test method.
• the foam containing a melamine based flame retardant and a flame retardant selected from FR1 14 FR9 exhibits excellent flame retardancy.
• Wire & cable grade polyethylene is dry blended with test additives and then melt compounded into pellets. The pelletized fully formulated resin is then extruded onto wire.
• Test specimens are tested for flame retardancy using the ASTM D 2633-82 burn test conditions.
• the formulations containing a melamine based flame retardant, a flame retardant selected from FR1–FR9 and optionally a compound selected from NOR1–NOR13 exhibit excellent flame retardancy.
• Fiber grade polyethylene is dry-blended with test additives.
• Non-woven fabrics are produced from the polymer blend formulations by a spun-bonded or melt-blown process.
• the non-woven fabrics made thereby are tested for flame retardancy according to the NFPA 701 vertical burn test specifications.
• the fabrics containing a melamine based flame retardant and a flame retardant selected from FR1–FR9 exhibit excellent flame retardancy.
• Fiber grade polypropylene is dry-blended with test additives.
• Non-woven fabrics are produced from the polymer blend formulations by a spun-bonded or melt-blown process.
• the non-woven fabrics made thereby are tested for flame retardancy according to the NFPA 701 vertical burn test specifications.
• the fabrics containing a melamine based flame retardant and a flame retardant selected from FR1–FR9 exhibit excellent flame retardancy.
• Molding grade polystyrene is dry-blended with test additives and then melt compounded. Specimens are injection molded from these test formulations.
• the specimens are tested for flame retardancy according to the UL-94 burn test specifications.
• the molded specimens containing a melamine based flame retardant and a flame retardant selected from FR1–FR9 exhibit excellent flame retardancy.
• Foam grade polystyrene is dry-blended with test additives and then melt compounded. Foam polystyrene-specimens are prepared from these test formulations.
• the specimens are tested for flame retardancy according to the UL-94 burn test specifications.
• the foam specimens containing a melamine based flame retardant and a flame retardant selected from FR1–FR9 exhibit excellent flame retardancy.
• ABS is dry blended with test additives and then melt compounded at 425° F. (218° C.). Specimens 125 mil (1 ⁇ 8′′) thick are then injection molded from this formulation using a Boy Injection Molder at 450° F. (232° C.). The specimens are tested for flame retardancy according to the UL-94 vertical burn test specifications.
• the specimens containing a melamine based flame retardant and a flame retardant selected from FR1–FR9 exhibit excellent flame retardancy.
• Fiber grade polypropylene is dry blended with test additives and then melt compounded at 234° C. (450° F.) into pellets.
• the pelletized fully formulated resin is then spun at 246° C. (475° F.) into fiber using a Hills laboratory model fiber extruder.
• the spun tow of 41 filaments is stretched at a ratio of 1:3.2 to give a final denier of 615/41.
• Socks are knitted from the stabilized polypropylene fiber on a Lawson-Hemphill-Analysis Knitter and tested under NFPA 701 vertical burn procedure. The time in seconds for the knitted sock to extinguish after the insult flame is removed is reported as “After Flame”. Both the maximum time for any one replicate and the total time for ten replicates are measured. Efficacy as a flame retardant is demonstrated when low After Flame times are observed relative to a blank sample containing no flame retardant.
• the specimens containing a melamine based flame retardant and a flame retardant selected from FR1–FR9 exhibit excellent flame retardancy.
• Film grade polyethylene is dry blended with test additives and then melt compounded into pellets.
• the pelletized fully formulated resin is then blown at 205° C. using a MPM Superior Blown film extruder.
• the films are tested for flame retardancy under NFPA 701 test conditions.
• the specimens containing a melamine based flame retardant and a flame retardant selected from FR1–FR9 exhibit excellent flame retardancy.
• TPO thermoplastic olefin
• the TPO formulations may also contain a pigment, a phosphite; a phenolic antioxidant or hydroxylamine, a metal stearate, a UV absorber or a hindered amine stabilizer or a mixture of hindered amine and UV absorber.
• Pigmented TPO formulation composed of polypropylene blended with a rubber modifier where the rubber modifier is an in-situ reacted copolymer or blended product containing copolymers of propylene and ethylene with or without a ternary component such as ethylidene norbornene are stabilized with a base stabilization system consisting of an N,N-dialkylhydroxyl-amine or a mixture of hindered phenolic antioxidant and an organophosphorus compound.
• a base stabilization system consisting of an N,N-dialkylhydroxyl-amine or a mixture of hindered phenolic antioxidant and an organophosphorus compound.
• the TPO plaques are tested for flame retardancy using the UL-94 Vertical Burn conditions. A minimum of three replicates are tested. Efficacy as a flame retardant is measured relative to a blank sample containing no flame retardant.
• the specimens containing a melamine based flame retardant and a flame retardant selected from FR1–FR9 exhibit excellent flame retardancy.
• EVA ethylene/vinyl acetate copolymers containing 20 weight percent or less of vinyl acetate are dry blended with test additives and then melt compounded into pellets. The pelletized fully formulated resin is then blown into a film at 205° C. using a MPM Superior Blown-film extruder.
• the films are tested for flame retardancy under NFPA 701 test conditions.
• the films containing a melamine based flame retardant and a flame retardant selected from FR1–FR9 exhibit excellent flame retardancy.
• LDPE Film grade low density polyethylene
• LLDPE linear low density polyethylene
• EVA ethylene/vinyl acetate
• High impact polystyrene (HIPS) polymer STYRON® 484C, Dow Chemical Co.
• STYRON® 484C Dow Chemical Co.
• test additives pelletized and then injection or compression molded into plaques. These plaques are tested for flame retardant efficacy using cone calorimetry, LOI or UL-94 test method.
• This Example shows the efficacy of the present compound combinations in PVC formulations. Such formulations are useful in flexible or rigid PVC and in wire and cable applications.
• Component parts parts parts parts PVC resin 100 100 100 100 100 100 tin mercaptide 1.5 — 2.0 — tin carboxyate — 2.5 — 2.0 process aid 1.5 1.5 2.0 2.0 impact mod. 6.0 7.0 7.0 paraffin wax 1.0 0.3 1.0 1.0 polyethyl wax 0.1 0.1 0.2 0.2 Ca stearate 1.0 — 0.8 — pigment 1.0 0.9 5.0 5.0
• Fully formulated PVC containing a melamine based flame retardant and a flame retardant selected from FR1–FR9 is pelletized and then injection molded into test plaques for examination of flame retardancy using the UL-94 or LOI test method.
• Fiber grade poly(ethylene terephthalate) (PET) is dry blended with test additives, then melt compounded at 550° F. and then pelletized. The polyester pellets are dried at 175° F. for 24 hours under vacuum. The dried pellets are extruded into fibers using a Hills laboratory scale fiber extruder at 550° F. Socks are knitted from these fibers and tested for flame retardancy according to NFPA 701 test method.
• PET Poly(ethylene terephthalate)
• the fibers containing a melamine based flame retardant and a flame retardant selected from FR1–FR9 exhibit excellent flame retardancy.
• Thermoplastic resins including polypropylene, polyethylene homopolymer, polyolefin copolymer or thermoplastic olefins (TPO), high impact polystyrene (HIPS) and ABS are dry blended with test additives and then melt compounded into pellets.
• TPO thermoplastic olefins
• HIPS high impact polystyrene
• ABS polystyrene
• Thermoplastic resins including polypropylene, polyethylene homopolymer, polyolefin copolymer or thermoplastic olefins (TPO), high impact polystyrene (HIPS) and ABS are dry blended with test additives and then melt compounded into pellets.
• TPO thermoplastic olefins
• HIPS high impact polystyrene
• ABS polystyrene
• Thermoplastic resins including polypropylene, polyethylene homopolymer, polyolefin copolymer or thermoplastic olefins
• the articles containing a melamine based flame retardant and a flame retardant selected from FR1–FR9 exhibit excellent flame retardancy when tested by a known standard test method.
• Polyethylene wire and cable applications are tested for flame retardancy according to ASTM D-2633-82 burn test method.
• the materials containing a melamine based flame retardant and a flame retardant selected from FR1–FR9 exhibit excellent flame retardancy.
• Articles prepared according to Example 19 which additionally contain an organophosphorus stabilizer selected from the group consisting of tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, 2,2′,2′′-nitrilo[triethyl-tris-(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite], tetrakis(2,4-di-butylphenyl) 4,4′-biphenylenediphosphonite, tris(nonylphenyl) phosphite, bis(2,4-di-tert-butylphenyl) pentaerythrityl diphosphite, 2,2′-ethylidenebis(2,4-di-tert-
• Articles prepared according to Example 19 which additionally contain a o-hydroxy-phenyl-2H-benzotriazole, a hydroxyphenyl benzophenone or a o-hydroxyphenyl-s-triazine UV absorber selected from the group consisting of 2-(2-hydroxy-3,5-di- ⁇ -cumylphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, 5-chloro-2-(2-hydroxy-3,5-di-tert-butyl-phenyl)-2H-benzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole, 2-(2-hydroxy-3- ⁇ -cumyl-5-tert-octylphenyl)-2H-benzotriazole, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-hydroxy-4-n
• Polypropylene homopolymer samples are prepared.
• the samples containing a melamine based flame retardant and a flame retardant selected from FR1–FR9 exhibit excellent flame retardancy when tested by a known standard test method.
• the parts containing a melamine based flame retardant and a flame retardant selected from FR1–FR9 exhibit excellent flame retardancy when tested by a known standard test method.
• Test method NFPA 701 is relevant.
• Example 23 is repeated with polystyrene electrical parts.
• the samples containing a melamine based flame retardant and a flame retardant selected from FR1–FR9 exhibit excellent flame retardancy when tested by a known standard test method.
• Test methods UL 94 and UL 1694 are relevant.

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